WO2010090522A2 - Method of preparing a liquid extract of cereal grain and apparatus suitable for use in such method - Google Patents
Method of preparing a liquid extract of cereal grain and apparatus suitable for use in such method Download PDFInfo
- Publication number
- WO2010090522A2 WO2010090522A2 PCT/NL2010/050052 NL2010050052W WO2010090522A2 WO 2010090522 A2 WO2010090522 A2 WO 2010090522A2 NL 2010050052 W NL2010050052 W NL 2010050052W WO 2010090522 A2 WO2010090522 A2 WO 2010090522A2
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- WO
- WIPO (PCT)
- Prior art keywords
- grain
- milling
- liquid
- blades
- cereal grain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02B—PREPARING GRAIN FOR MILLING; REFINING GRANULAR FRUIT TO COMMERCIAL PRODUCTS BY WORKING THE SURFACE
- B02B1/00—Preparing grain for milling or like processes
- B02B1/04—Wet treatment, e.g. washing, wetting, softening
- B02B1/06—Devices with rotary parts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02B—PREPARING GRAIN FOR MILLING; REFINING GRANULAR FRUIT TO COMMERCIAL PRODUCTS BY WORKING THE SURFACE
- B02B1/00—Preparing grain for milling or like processes
- B02B1/04—Wet treatment, e.g. washing, wetting, softening
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C18/00—Disintegrating by knives or other cutting or tearing members which chop material into fragments
- B02C18/06—Disintegrating by knives or other cutting or tearing members which chop material into fragments with rotating knives
- B02C18/08—Disintegrating by knives or other cutting or tearing members which chop material into fragments with rotating knives within vertical containers
- B02C18/10—Disintegrating by knives or other cutting or tearing members which chop material into fragments with rotating knives within vertical containers with drive arranged above container
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C18/00—Disintegrating by knives or other cutting or tearing members which chop material into fragments
- B02C18/06—Disintegrating by knives or other cutting or tearing members which chop material into fragments with rotating knives
- B02C18/16—Details
- B02C18/18—Knives; Mountings thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C18/00—Disintegrating by knives or other cutting or tearing members which chop material into fragments
- B02C18/06—Disintegrating by knives or other cutting or tearing members which chop material into fragments with rotating knives
- B02C18/16—Details
- B02C18/22—Feed or discharge means
- B02C18/2216—Discharge means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C18/00—Disintegrating by knives or other cutting or tearing members which chop material into fragments
- B02C18/06—Disintegrating by knives or other cutting or tearing members which chop material into fragments with rotating knives
- B02C18/16—Details
- B02C18/22—Feed or discharge means
- B02C18/2225—Feed means
- B02C18/2258—Feed means of screw type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C21/00—Disintegrating plant with or without drying of the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C25/00—Control arrangements specially adapted for crushing or disintegrating
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C7/00—Preparation of wort
- C12C7/01—Pretreatment of malt, e.g. malt grinding
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C7/00—Preparation of wort
- C12C7/04—Preparation or treatment of the mash
- C12C7/042—Mixing malt with water
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C7/00—Preparation of wort
- C12C7/04—Preparation or treatment of the mash
- C12C7/06—Mashing apparatus
- C12C7/065—Mashing apparatus with a vertical stirrer shaft
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C7/00—Preparation of wort
- C12C7/14—Lautering, i.e. clarifying wort
Definitions
- the present invention relates to a method of preparing a liquid extract of cereal grain.
- the method according to the present invention may, for instance, suitably be used in the brewing industry, e.g for wort production.
- the invention further provides a system comprising a milling apparatus and a separation device suitable for use in the aforementioned method.
- ⁇ conditioned milling similar to dry milling by roller mill, except that malt moisture level is raised slighlty to make the husks of the grains more pliable.
- the inventors have discovered that the aforementioned objective is met by a continuous milling method in which cereal grain particles are disintegrated whilst being suspended in a liquid, said disintegration being achieved by colliding freely suspended grain particles with one or more blades that are rotating at a very high tip speed of at least 10 m/s.
- the distance between a tip of said one or more rotating blades and the axis of rotation is in the range of 2-25 cm and the total mechanical energy transferred by the one or more rotating blade is in the range of 5- 1000 kJ per kg of dry cereal grain.
- the present method employs one or more relatively small rotating blades that rotate at very high speed and that remain in contact with the suspension containing the cereal grain particles for a sufficiently long period of time to achieve a significant particle size reduction.
- the method according to the present invention provides all the benefits of wet milling, is no more complex than a hammer mill and extremely robust.
- the present method utilises the same principle that is applied in standard kitchen blenders, i.e. a blade rotating at very high speed. Due to the inertia of the suspended cereal grain particles, the fast rotating blade is capable of disintegrating these grain particles on impact. Unlike the milling techniques that have so far been used to comminute cereal grains on an industrial scale, the disintegration of the grain particles in the present method does not rely on stressing of the grain particles between two solid surfaces.
- a system for preparing liquid extract of cereal grain comprising a milling apparatus and a separation device for separating spent grain and liquid extract connected downstream to the milling apparatus, wherein the milling apparatus comprises a liquid inlet connected to a milling chamber for containing a milled suspension, wherein a rotor is received in the milling chamber, the rotor comprising one or more blades extending from the axis of rotation of the rotor, the blade being received in the milling chamber, wherein a distance between a tip of said one or more blades and the axis of rotation is in the range of 2-25 cm, the rotor being connected to a driving unit for rotation, wherein the driving unit is arranged to drive the blade at a tip speed of at least 10 m/s.
- the present method can also suitably be used to mill and extract cereal grains with a moisture content exceeding 12%.
- the present method when used to extract e.g. barley, yields a liquid extract having a reduced ⁇ -glucan content. This reduction of ⁇ -glucan levels has a positive effect on product quality as well as on downstream processing.
- the benefits of the present method are particularly pronounced when employed in industrial scale production of liquid extracts from cereal grain.
- the present method is advantageously employed to prepare a liquid extract of cereal grain by processing cereal grain at a rate of at least 100 kg of dry cereal grain per hour.
- Figure 1 schematically shows a first embodiment of a system according to the invention.
- Figure 2 schematically shows a second embodiment of a system according to the invention.
- Figures 3 a and 3b schematically show a detail of a blade according to an embodiment of the invention.
- Figure 4 schematically shows a third embodiment of a system according to the invention.
- Figure 5 schematically shows an alternative arrangement of a milling apparatus according to the invention.
- one aspect of the invention relates to a continuous method of preparing a liquid extract of cereal grain by comminuting cereal grain at a rate of at least 100 kg of dry cereal grain per hour and extracting the comminuted cereal grain with a liquid, said method comprising: - continuously combining cereal grain with a liquid; continuously disintegrating the grain particles contained within the liquid by colliding freely suspended grain particles with one or more rotating blades, thereby producing a milled suspension; continuously transferring at least a part of the milled suspension, optionally after further treatment, to a separation device for separation into spent grain and liquid extract; wherein the one or more rotating blades are rotating at a tip speed of at least 10 m/s; the total mechanical energy transferred into the milled suspension by the one or more rotating blades is in the range of 5-1000 kJ per kg of dry cereal grain; and the distance between a tip of said one or more rotating blades and the axis of rotation is in the range of 2-25 cm.
- the term "cereal grain” as used herein refers to a particulate form of a cereal crop, a fruitseed (caryopsis), or a combination of two or more of these materials.
- the present invention encompasses a method in which the cereal grain employed is a pre- milled cereal grain.
- the term "blade” as used herein refers to a solid object that is configured to rotate about an axis of rotation, and that normally includes at least two (blade) wings radially extending in different, e.g. opposite directions from a centre (of gravity) point.
- One requirement of the blade is that it can suitably be used for disintegrating the grain particles upon impact.
- the blade is required to provide agitating action in order to blend the cereal grain with the liquid, thereby assisting in the uniform comminution of the grain particles.
- disintegrate refers to the breaking up of a solid particle into two or more solid particles.
- disintegrate does not encompass the breaking up of loosely bound particles, such as agglomerates.
- mechanical energy refers to the total amount of potential energy and kinetic energy that is transferred into the milled suspension by the one or more rotating blades.
- the amount of mechanical energy that is transferred in the present method can be deduced from e.g. the temperature increase caused by the rotating blades and/or it can be calculated from torque that is employed to rotate the blades.
- one or more rotating blades is to be understood to refer to blades that are moving through the liquid containing the grain particles in a rotating path.
- the one or more rotating blades are mounted on a rotating axis or on a rotating body (e.g. on the inside of rotating cylinder).
- the one or more rotating blades are mounted on a stationary body and the liquid containing the grain particles is caused to rotate past the blades, e.g. under the influence of rotating paddles
- it is also feasible to enhance the efficacy of the present method by employing blades that are mounted on a rotating body and by causing the liquid to rotate in a direction that is opposed to the direction in which the blades rotate.
- the present method is carried out in a continuous fashion, which means that the present process employs an essentially continuous stream of cereal grain and an essentially continuous stream of liquid or alternatively an essentially continuous stream comprising cereal grain and liquid, and furthermore that it yields an essentially continuous stream of milled suspension.
- the part of the milled suspension that is transferred to a separation device is advantageously continuously separated into liquid extract and spent grain.
- the liquid extract so obtained can suitably be employed in a batch-wise or continuously operated process, e.g. a brewing process.
- the present method can be used in a brewing process that employs batch operations such as batch wort production and batch fermentation.
- the present method is employed in a continuous brewing process that additionally includes continuous wort boiling, continuous trub removal and continuous fermentation.
- a system for preparing ajiquid extract of cereal grain, said syst ⁇ rn_bcir]g_suj ⁇ ablc ⁇ is provided.
- the system comprises a milling apparatus and a separation device for separating spent grain from liquid extract connected downstream to the milling apparatus, wherein the milling apparatus comprises a liquid inlet connected to a milling chamber for containing a milled suspension, wherein a rotor is received in the milling chamber, the rotor comprising one or more blades extending from the axis of rotation of the rotor, the blades being received in the milling chamber, wherein a distance between a tip of said one or more blades and the axis of rotation is in the range of 2-25 cm, the rotor is connected to a driving unit for rotation, wherein the driving unit is arranged to drive the blade at a tip speed of at least 10 m/s.
- the present method and system can suitably be operated on an industrial scale.
- the cereal grain is comminuted at a rate of at least 150, preferably 200, more preferably of at least 300 kg of dry cereal grain per hour.
- the present method and system offer the advantage that size reduction of the grain particles can be achieved solely by the action of the fast rotating blade(s).
- wear and tear as a result of direct or indirect contact between different elements of a milling device, e.g. as a result of foreign objects such as stones, are minimised.
- the disintegration of the grain particles under the action of the one or more rotating blades does not result from stressing the grain particles between a surface of said one or more rotating blades and another solid surface.
- this feature distinguishes the present method from wet milling techniques such as wet milling by steeping and roller mill, conditioned milling and dispersion pump milling.
- the present method and system can advantageously be used to achieve a substantial reduction of the particle size of the cereal grain particles.
- the disintegration of the grain particles under the action of the one or more rotating blades causes a reduction of the mass weighted average particle size of the cereal grain by at least a factor 2, preferably by at least a factor 4.
- the one or more rotating blades cause a reduction of said average particle size by at least a factor 8.
- the present method and system can suitably be used to prepare a liquid extract from a wide variety of cereal grain materials.
- the grain particles contained within the liquid have a mass weighted average particle size of 0.5 mm to 1 cm, preferably of 1 mm to 8 mm.
- the present method and system typically yields a milled suspension wherein the particles have a mass weighted average diameter in the range of 50-1000 ⁇ m, preferably in the range of 100-800 ⁇ m.
- large (coarse) particles e.g. particles having diameter of at least 0.5 mm are selectively removed from the milled suspension during or after the milling operation and before it reaches the separation device, by passing the liquid suspension through a suitable separation element, e.g. a sieve, a screen or a hydrocyclone.
- a suitable separation element e.g. a sieve, a screen or a hydrocyclone.
- the terms "selectively removed” or “selectively separated” means that the coarse particles are removed and that smaller particles remain in the suspension. Even more preferably, particles having a diameter of at least 1.0 mm are removed from the milled suspension. Most preferably, particles having a diameter of at least 2.0 mm are removed.
- the large particles removed from the milled suspension are preferably recirculated to the milling step, notably by introducing these separated particles into the liquid containing the suspended grain particles.
- the separated particles are recirculated in a continuous fashion.
- a feedback loop can be provided from downstream of the milling apparatus to upstream of the milling apparatus.
- a return conduit can return suspension containing large particles to at least one milling apparatus according to the present invention. It should be understood that the latter embodiment includes recirculation of the separated particles directly to the milling apparatus or upstream of the milling apparatus (e.g. to a mixing device in which the grain particles feed is combined with the liquid).
- the liquid and cereal grain are suitably combined in the present method to form a suspension containing 6-50 wt.%, preferably 10-45 wt.% and most preferably 15-40 wt.% of dry matter.
- dry matter includes both dissolved and non-dissolved material.
- the liquid that is combined with the cereal grain preferably is an aqueous liquid.
- the aqueous liquid employed can be brewing water.
- the present invention also encompasses the use of a recirculated aqueous liquids stream that originates from elsewhere in the brewing process.
- An example of such a recirculated aqueous liquid is washing water that has been used in the present method to wash spent grain.
- the milling efficiency of the present method and system are affected by the volume of the chamber in which the disintegration of the grain particles under the action of the rotating blades occurs. If the volume is large, it may take unacceptably long to achieve a substantial particle size reduction. If the volume is very small it will also be difficult to achieve a substantial particle size reduction as the residence time will be so short that only a fraction of the grain particles will have chance to collide with the rotating blades.
- the inventors have discovered that very efficient comminution of the cereal grain can be achieved by passing the combined stream of cereal and liquid through a sequence of chambers of relatively small volume, wherein each chamber contains one or more rotating blades as defined herein before.
- efficient milling can be achieved by passing the combined stream through a tube containing a sequence of two or more, preferably of a sequence of three or more rotating blades.
- the tube can be straight, but it may also be curved.
- the cross-section of the tube can take several shapes, e.g. circular or squarish.
- the grain particles are disintegrated by passing the liquid holding the grain particles through two or more, even more preferably through three or more comminution chambers that each contain one or more of the rotating blades.
- the residence time within each of the comminution chambers preferably is within the range of 0.1-10 minutes, more preferably within the range of 0.1-4 minutes.
- the residence time within each of the comminution chambers is in the range of 0.2-2 minutes.
- the rotating blades employed in the present method and system are suitably mounted onto a fast rotating shaft.
- the present method and system employ one or more rotating blades that each comprise at least two blade wings that radially extend in different, e.g. opposite directions from a gravitational centre point that coincides with the rotational axis.
- the wings of the rotating blades include leading edges and trailing edges. Preferably, at least a part of the leading edges of the blade wings is bevelled to provide a cutting edge. By providing the leading edges of the wings with a cutting edge the effectiveness of the rotating blades in disintegrating the grain particles can be further improved.
- the one or more blades employed in the present method and system advantageously provide an agitation action during operation.
- the (cutting) edges of the blades define a cutting path, and the wings generate flow of the liquid and the grain particles.
- the flow generated by the wings due to rotation of the one or more blades draws the liquid and suspended grain particles through the cutting path to homogeneously mix these components, and to disintegrate the grain particles entrained in the liquid using the cutting blades.
- the one or more rotating blades act as stirring propellers, i.e. the blades act as rotating wings and generate a difference in pressure between the forward and rear surfaces of the blades.
- the stirring action of the blades disintegrated particles will be pushed away by the rotating blades so they can be replaced by other particles.
- the one or more blades comprise at least two blade wings that are twisted, pitched or otherwise shaped such that the leading edges are vertically oriented above or below the trailing edges (when the rotational axis is vertical). If, for instance, the blade wings are twisted such that the leading edges are vertically oriented above the trailing edges, then rotation of the blender blade repeatedly draws the liquid (including the grain particles) through the cutting path. As such, rotation of the blender blade continuously draws the grain particles downwardly through the cutting path, and thereafter, pushes the particles upwardly along the interior surface of the comminution chamber. Consequently, the grain particles and liquid are homogeneously mixed because the grain particles are continually ground and mixed with the contents of the comminution chamber through rotation of the blade.
- the one or more blades comprise two or more wings whose leading edges define cutting paths and wherein said blade wings are oriented at compound angles with respect to the plane that runs perpendicular to the axis of rotation through the gravity centre of the blades so as to provide the blender blade with compound cutting paths.
- each of the wings is twisted or otherwise shaped such that its leading edge is vertically oriented above or below its trailing edge, and angled such that its distal end is vertically oriented above or below the centre point (when the rational axis is vertical).
- the leading edge of the blade wings is vertically oriented above its trailing edge and its distal end is vertically oriented above or below the centre point.
- the blade wings may be twisted along the full length of the wing or, alternatively, a part of the blade wings can be twisted in order to generate adequate lift.
- the angle of the slope from the leading edge to the trailing edge of the blade wings does not exceed 60°, more preferably it does not exceed 45° (the angle of slope being defined relative to a horizontal plane, assuming a vertical rotational axis).
- the maximum angle of the slope from the leading edge to the trailing edge is in the range of 5-30°.
- the blade wings employed in the present process advantageously extend radially outwards from a rotating axis.
- the blade wings can extend outwards at an upward or downward angle relative to the radial plane.
- This upward or downward angle relative to the radial plane preferably is within the range of 5-70°, more preferably within the range of 10-45°.
- a tip portion of the wing is tilted with respect to the radial plane at the aforementioned angles.
- said tip portion represents less than 60%, more preferably less than 50% of the length of the blade wing.
- the one or more rotating blades comprise two or more blade wings extending in the same radial direction at different upward and downward angles.
- This arrangement of the blade wings offers the advantage that it increases the efficiency of the milling action.
- Each of the blade wings has an effective width and a length measured between the axis of rotation and the distal ends of the wing tips, the ratio of the effective width to the length of the wings being in the range of 1 : 1 tol :20, preferably in the range of 1 :2-1 :15.
- the rotating blades employed in the present method and system are rotating at very high speed.
- the one or more rotating blades are rotating at a speed of at least 2,000 rpm, more preferably of at least 10,000 rpm.
- the tip speed of the one or more rotating blades typically is at least 12 m/s, more preferably at least 15 m/s, more preferably at least 20 m/s, even more preferably at least 50 m/s and most preferably at least 70 m/s.
- the benefits of the present invention are achieved by employing rotating blades of relatively small dimensions.
- the length of the blade is bound to a maximum as the torque needed to rotate the blade at high tip speed increases exponentially with increasing blade length and also because long blades are much more vulnerable when operated at high rpm.
- the distance between a tip of the one or more rotating blades employed in the present method and the axis of rotation i.e.
- the length of said one or more blades is within the range of 2.5-20 cm, more preferably within the range of 2.5-18 cm and most preferably within the range of 3-15 cm.
- the tips of all the rotating blades that rotate at a tip speed of at least 10 m/s, especially at a tip speed of at least 20 m/s are located within 25 cm, more preferably within 20 cm, even more preferably within 18 cm and most preferably within 15 cm of the axis of rotation.
- the present method can be operated with little maintenance, it is advisable to employ rotating blades that are made of a shear resistant material selected from the group consisting of metals, ceramics, synthetic polymers, diamond and combinations thereof.
- the one or more rotating blades have a thickness of 0.1-1 cm, more preferably of 0.2-0.8 cm and most preferably of 0.25-0.6 cm. It is advantageous to employ a blade of minimal thickness as this minimises rotational friction and maximizes the 'cutting' capability of the blade. Naturally, however, the thickness should be sufficient to warrant an adequate operational lifetime of the rotating blade.
- the temperature of the liquid that is combined with the cereal grain prior to disintegration by the action of the rotating blades can vary within a wide range.
- the temperature of the liquid when it is combined with the cereal grain is within the range of -5 to 100 0 C, preferably within the range of 10-60 0 C.
- the total amount of mechanical energy that transferred into the milled suspension by the one or more rotating blades is at least 8, more preferably at least 10 and most preferably at least 15 kJ per kg of dry cereal grain.
- the present method offers the advantage that considerable size reduction of the cereal grain can be achieved with a limited amount of mechanical energy transfer. Accordingly, the total mechanical energy transferred into the milled suspension by the one or more rotating blades advantageously does not exceed 800, more preferably does not exceed 500, more preferably does not exceed 300 kJ per kg of dry cereal grain.
- the mechanical energy transferred into the milled suspension by the one or more rotating blades in the absence of cooling or significant evaporation, will cause a temperature increase of the milled suspension.
- the disintegration of the grain particles is typically accompanied by a temperature increase of the milled suspension of less than 100 0 C, more preferably of less than 60 0 C, and most preferably of less than 30 0 C.
- the suspension of grain particles may be cooled during the milling operation. According to a preferred embodiment, however, the disintegration of the grain particles is achieved without cooling the suspension.
- the milled suspension may suitably be subjected to one or more further treatments before being transferred to a separation device for separation into spent grain and liquid extract.
- a separation device for separation into spent grain and liquid extract.
- the milled suspension prior to separation into spent grain and liquid extract, is subjected to a mashing operation to allow enzymes to break down extracted starch into sugars, typically maltose.
- Separation into spent grain and liquid extract may suitably be achieved any solid-liquid separation technique known in the art.
- said separation is achieved by means of one or more separation devices selected from a mash filter, a centrifuge, a lautertun, a sieve.
- the present method is particularly suited for preparing a milled suspension that can be separated very efficiently by means of a mash filter.
- the present method employs a mash filter to separate the milled suspension into a spent grain and liquid extract.
- the cereal grain of the present method includes barley, especially malted barley.
- Figure 1 schematically shows a first embodiment of a system according to an embodiment of the invention
- Figure 2 schematically shows a second embodiment
- FIGS. 3 a and 3b schematically show a detail of a blade according to an embodiment of the invention
- Figure 4 schematically shows a third embodiment
- Figure 5 schematically shows an alternative arrangement of a milling apparatus according to the invention.
- Figure 1 provides a schematic example of an embodiment of the invention.
- the Figure shows a cross section of a milling apparatus 1.
- Further Figure 1 schematically shows a reactor 50 (e.g. a heat exchanger) and a separation device 20 (e.g. a device for separating solids from liquid) according to the invention.
- a system comprising the milling apparatus 1, a reactor 50 and a separation device 20 can be used in the preparation and production of a liquid extract of a cereal grain, such as wort.
- the system according to the invention comprises one or more milling apparatuses 1.
- the system according to the invention comprises a series of two or more milling apparatuses 1.
- the two or more milling apparatuses 1 are preferably connected in series. It is also feasible to employ one milling apparatus containing a sequence of rotating blades, e.g. by using a tube holding two or more rotatable blades.
- the use of two or more milling apparatuses or of using a sequence of rotating blades enables efficient disintegration of the grain particles, as will be explained in more detail hereunder.
- a liquid is introduced into a milling apparatus 1 through an inlet 2 into a milling chamber 3.
- the milling chamber 3 is a vessel or container.
- a second inlet 4 schematically represents the inlet for feeding cereal grain into the milling chamber 3.
- the inlets 2,4 are shown at a specific position, the skilled person is capable of positioning the inlets 2,4 at desired positions.
- one of the inlets brings the liquid or cereal grain into a middle portion of a milling chamber 3, e.g. close to blades 30,31.
- a mixture of liquid and cereal grain is introduced in milling apparatus 1 through inlet 2.
- the milling chamber 3 contains a suspension of cereal grain.
- the suspension is shown in the Figure having a fluid level 13.
- the milling chamber 3 is completely filled with fluid. It is possible to control the inflow of liquid and cereal grain into the milling chamber.
- Parameters representing the amounts of inflow can be collected in a controller 5 comprising a processor and memory (not shown).
- the controller 5 is connected, e.g. wireless, with a measuring device (not shown) for measuring the amount of inflow.
- the regulating valve 44 as well as the dosing screw 45 can comprise a means for controlling the amount of inflow into the milling chamber 3.
- the controller 5 is connected with and can control a driving unit 6.
- Driving unit 6 schematically represents a unit that is capable of bringing rotor 7 into rotation at a desired speed.
- Driving unit 6 can be an electronically controlled engine. It can comprise a transmission.
- Rotor 7 comprises a shaft 8 that extends into the milling chamber 3 suspended in schematically represented sealed shaft bearing 12.
- the driving unit 6 is also received in the milling chamber 3.
- a transmission is received in the milling chamber 3.
- the rotation axis of the driving unit 6 is connected to the shaft
- one driving unit 6 can be used to drive more than one shaft 8 of different milling apparatuses 1.
- one milling apparatus 1 comprises more than one shaft 8 having different blades 30,31.
- Two blades 30,31 are mounted on shaft 8.
- a blade 30,31 is a replaceable unit that can be locked and unlocked onto shaft 8.
- a sleeve 46 is interpositioned between the blades 30,31. The skilled person will be able to arrange different kinds of mounting systems for mounting and locking a blade 30,31 to the shaft 8.
- blade 30 comprises three blade wings 9-11, as is shown in the embodiment of Figure 3b.
- the distance 15 from the axis of rotation 14 to the tip 16 of a blade is at least 2 cm.
- the distance 15 is at least 5 cm and more preferably at least 10 cm.
- the blades have a maximum length 15 of at most 25 cm, more preferably at most 20 cm.
- the blade 30 is arranged and constructed for rotation in a clockwise direction 28 as a sharp edge 29 will form the front edge of wings 9-11 during rotation.
- the distal portion 27 of wings 9-11 comprises an upwardly bended fin 26. Fins 26 and sharp front edges 29 are arranged and constructed for pulverizing the grains present in the fluid contained in the milling chamber. Fins 26 are further arranged and constructed for stirring the fluid in operation.
- tip 16 will have a minimum speed of at least 10 m/s in order to create a blender-like effect during milling.
- Blade 90 comprises a central sleeve like body 91 having four wings 92-95 extending radially from the sleeve like body 91.
- Each wing 92-95 comprises a generally radially extending portion 96 and a tip portion 97, more distal from the portion 96 that extends under an angle ⁇ upwards or downwards with respect to the radial plane 98.
- the wings 92-95 are also provided with a fin. This is not shown in Figure 3a.
- the fin, or another part of the wing extending in a direction parallel to the shaft axis 14, can cause a disturbance in the fluid during rotation, causing mixing of the fluid in use, allowing milling of the complete fluid contained within the milling chamber 3.
- the fins are arranged and constructed for causing a suction and pushing of fluid to and from the wing during rotation thereof to cause stirring in the fluid.
- the shaft 8 extends from a bottom end of the milling chamber
- the blades extend from the shaft close to a bottom surface of the milling chamber.
- the controller 5 can control driving unit 6 to bring the blades into rotation.
- the driving unit is capable of rotating the tip 16 of the blade wings at at least 10 m/s, preferably at least 15 m/s. This will allow to obtain a kitchen blender effect at an industrial scale, which results in a system of preparing a liquid extract of cereal grain by comminuting cereal grain at a rate of at least 100 kg of dry cereal grain per hour being more effective than prior art systems.
- the apparatus 1 is arranged for continuous feed of liquid and cereal grain.
- FIG. 2 shows a different embodiment, wherein a mixing chamber 60 is arranged upstream from a series of three milling apparatuses 61 and wherein other elements are similar to the first embodiment.
- Mixing chamber 60 comprises two inlets 62,63 for cereal grain and for water or an aqueous liquid, which are brought together in a generally drum shaped container comprising a mixing device 64 illustrated schematically.
- the mixing device comprises a blade 65 and a driving unit 66.
- Driving unit 66 and blade 65 are arranged to mix the fluid and grain.
- a preferably low RPM is used for mixing.
- the mixing chamber 60 is arranged to perform a milling pre-processing of the suspension.
- the mixed suspension flows to a first of three milling apparatuses 61 which have a similar set up as milling apparatus 1.
- the blades 30,31 and in particular the tips 16 of blade wings 9-11 will disintegrate grain particles suspended in the liquid contained in the milling chamber 3.
- the blade wings will, due to the high angular velocity and in particular due to the high speed of the tips 16 of the blade wings 9-11, transfer a substantial amount of kinetic energy into the suspension.
- the total mechanical energy transferred is at least 5 kJ per kg of dry cereal grain.
- the controller 5 is capable of monitoring that the speed of rotation is sufficient for transferring the suitable amount of kinetic energy into the suspension, i.e. sufficient kinetic energy to disintegrate grain particles in the suspension.
- the milling chamber could comprised one or more baffles 74,75 that extend in the shown embodiment radially inward from the milling chamber 3 wall.
- the baffles 74,75 can be part of a baffle body that is positioned in the milling chamber 3.
- the first milling apparatus shown in Figure 1 has an outlet 18.
- the outlet 18 can comprise a valve 19 (or a pump), which can be controlled by controller 5.
- the outlet 18 allows transport of the grain suspension to the next milling apparatus.
- the last milling apparatus has an outlet 21 which allows transport of the milled suspension to a reactor chamber 50 and further downstream to a separation device 20.
- Separation device 20 in this embodiment comprises a schematically illustrated mesh 22 upstream from outlet 23.
- the separation device 20 further comprises a centrifuge.
- a centrifuge The skilled person in the preparation of liquid extracts of cereal grains will be familiar with different setups that can be used in combination with a milling apparatus according to the shown embodiment.
- the outlet 18 is positioned generally at half-way height of the milling chamber 3. This will allow continuous transfer of milled fluid from the chamber 3. Near the bottom side the more heavier suspended particles will collect, while near a higher end there will be less suspended particles.
- Figure 1 shows a liquid level 13, it is also possible and in some embodiments preferred to operate the chambers without a gaseous phase of headspace present in the milling apparatus 1.
- the transfer between the milling apparatuses 1,61 and towards a reaction chamber 50 is continuous. Subsequent transfer steps could be both batch and/or continuous.
- Figure 1 illustrates the system according to the invention in a very schematic way
- the skilled person will be able to upgrade the shown embodiment to an industrial scale, using the invention as disclosed herein.
- the skilled person is capable of providing the system according to the invention in a brewery.
- Figure 4 schematically illustrates a third embodiment of a system according to the invention.
- Figure 4 schematically shows a system comprising a mixing apparatus 100 and a milling apparatus 104, wherein said milling apparatus comprises a single milling chamber 105, wherein three schematically illustrated driving units and rotors 101,102,103 are received.
- Cereal grain 120 and water or an aqueous liquid 121 is added to the mixing chamber 112 to be converted into a suspension.
- Mixing apparatus 100 comprises a rotor 111 received in mixing chamber 112, wherein also driving unit 113 connected to the rotor 111 is completely received in the mixing chamber 112.
- Milling chamber 105 comprises three milling units 106-108 separated schematically by partitioning panels 109,110.
- the partitioning panels 109,110 are advantageously arranged in such a way that large (or coarse) particles contained in the suspension flowing through the milling chamber 105 are retained in milling units 106 and 107 respectively.
- the large particles are retained by the partitioning panels 109 and 110 because the suspension level 122 in the mixing chamber 105 is sufficiently high to allow the suspension to overflow these panels into the next milling unit but not high enough to carry with it the large particles contained therein.
- large particles are retained in milling unit 106 and milling unit 107 until they have been disintegrated by the milling action to a particle size that can pass partitioning panel 109 or partitioning panel 110.
- FIG. 5 illustrates a different embodiment of a milling apparatus 130.
- a driving unit 131 is connected to a frame, not shown. Further, stationary element 135 is connected fixedly to that frame. Driving unit 131 drives rotor body 133 carrying blades 136 into rotation according to arrow 138. Rotor body 133 is mounted rotatable 134 onto stationary element 135. Here the stationary element 135 is positioned at the position of the axis of rotation. The tip of the blades 136 is positioned near 139.
- a continuous stream of 128 kg/h of malt was introduced into a milling chamber together with a continuous stream of 283 kg/h brewing water.
- a blade with a diameter of 8.5 cm rotated at 21,500 rpm.
- the product stream from this chamber was transferred to 2 similar chambers operated in series at identical process settings. This milling system was brought to steady state by milling for at least 20 min. at constant infeed conditions.
- Product from the third milling chamber was collected and poured into a 100 L stirred mashing vessel.
- a typical mashing profile was used with: a 20 min. protein rest at 58°C, a heating phase to achieve 66°C in 15 min., a saccharification rest at 66°C for 25 min., again heating for 15 min to 76°C and a final rest at this temperature for 10 min.
- the mash was transferred to a 2-chamber mash filter. The mash filter was operated in the same fashion as with hammer milled malt.
- the resulting wort was pumped towards a boiling vessel and the wort was boiled for 90 min. After separation of hot trub and wort cooling to fermentation temperature, oxygen and yeast was added and a normal beer fermentation was performed. Wort samples were drawn and analysed, indicating an original gravity of the wort of 12.9% (w/w).
- Final beer product was packaged in suitable containers (bottles) and analysed on beer quality parameters. Analysis on wort parameters and beer parameters indicated good mashing performance and good product quality. Of particular interest is the amount of fermentable sugars formed during the mashing process, indicating the availability of starch for enzymatic induced by the milling of the malt grains. In this example, a value of 69.8 % (w/w) of the carbohydrates were fermentable sugars, resulting in an apparent final attenuation limit of 86% (w/w).
- Continuous streams of 200 kg/h of malt and 400 kg/h water are introduced into a mixing vessel, continuously stirred with an impeller to obtain a suspension.
- the mixture is transferred into a first milling chamber having a volume of 6 L.
- a blade with a diameter of 8.5 cm is rotated continuously at 21,500 rpm in the chamber.
- the product stream from this chamber is transferred to two similar chambers operated in series at identical process settings.
- a positive displacement pump transfers the mixture into a vertical conversion reactor of 600 L volume.
- the reactor is fitted with a vertical axis on which discs are mounted to achieve mixing.
- a temperature profile along the height of the reactor is applied with a protein rest at 58°C, a saccharification rest at 67°C, and a final rest at 78°C.
- the mash is transferred to a decanter centrifuge to remove particles.
- the resulting wort is pumped towards a boiling reactor of the same geometry as the conversion reactor and the wort is boiled for 60 min at 103 0 C. After separation of hot trub and wort cooling to fermentation temperature, oxygen and yeast are added and a normal beer fermentation is performed.
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- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Disintegrating Or Milling (AREA)
- Cereal-Derived Products (AREA)
- Mixers Of The Rotary Stirring Type (AREA)
- Crushing And Pulverization Processes (AREA)
- Separation Of Solids By Using Liquids Or Pneumatic Power (AREA)
- Crushing And Grinding (AREA)
- Adjustment And Processing Of Grains (AREA)
- Beans For Foods Or Fodder (AREA)
Abstract
Description
Claims
Priority Applications (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK10704007.3T DK2393911T3 (en) | 2009-02-05 | 2010-02-05 | PROCEDURE FOR PREPARING A FLUID EXTRACTION OF GRAIN AND APPLIANCES SUITABLE FOR USE IN SUCH A PROCEDURE |
| HRP20130104AT HRP20130104T1 (en) | 2009-02-05 | 2010-02-05 | Method of preparing a liquid extract of cereal grain and apparatus suitable for use in such method |
| PL10704007T PL2393911T3 (en) | 2009-02-05 | 2010-02-05 | Method of preparing a liquid extract of cereal grain and apparatus suitable for use in such method |
| CN2010800068752A CN102307982B (en) | 2009-02-05 | 2010-02-05 | Method of preparing a liquid extract of cereal grain and apparatus suitable for use in such method |
| ES10704007T ES2402710T3 (en) | 2009-02-05 | 2010-02-05 | Method for preparing a liquid cereal grain extract and apparatus suitable for use in said method |
| BRPI1008871-7A BRPI1008871A2 (en) | 2009-02-05 | 2010-02-05 | Continuous method and suitable system for preparing liquid cereal grain extract |
| CA2751428A CA2751428A1 (en) | 2009-02-05 | 2010-02-05 | Method of preparing a liquid extract of cereal grain and apparatus suitable for use in such method |
| US13/147,783 US9180462B2 (en) | 2009-02-05 | 2010-02-05 | Method of preparing a liquid extract of cereal grain and apparatus suitable for use in such method |
| JP2011549106A JP5599825B2 (en) | 2009-02-05 | 2010-02-05 | Method for producing a cereal extract and apparatus suitable for use in this method |
| EP10704007A EP2393911B1 (en) | 2009-02-05 | 2010-02-05 | Method of preparing a liquid extract of cereal grain and apparatus suitable for use in such method |
| SI201030140T SI2393911T1 (en) | 2009-02-05 | 2010-02-05 | Method of preparing a liquid extract of cereal grain and apparatus suitable for use in such method |
| EA201171003A EA018932B1 (en) | 2009-02-05 | 2010-02-05 | Method of preparing a liquid extract of cereal grain and apparatus suitable for use in such method |
| KR1020117020757A KR101770357B1 (en) | 2009-02-05 | 2010-02-05 | Method of preparing a liquid extract of cereal grain and apparatus suitable for use in such method |
| MX2011008274A MX2011008274A (en) | 2009-02-05 | 2010-02-05 | Method of preparing a liquid extract of cereal grain and apparatus suitable for use in such method. |
| ZA2011/05583A ZA201105583B (en) | 2009-02-05 | 2011-07-28 | Method of preparing a liquid extract of cereal grain and apparatus suitable for use in such method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09152147 | 2009-02-05 | ||
| EP09152147.6 | 2009-02-05 |
Publications (2)
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| WO2010090522A2 true WO2010090522A2 (en) | 2010-08-12 |
| WO2010090522A3 WO2010090522A3 (en) | 2011-04-07 |
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ID=40934970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/NL2010/050052 Ceased WO2010090522A2 (en) | 2009-02-05 | 2010-02-05 | Method of preparing a liquid extract of cereal grain and apparatus suitable for use in such method |
Country Status (20)
| Country | Link |
|---|---|
| US (1) | US9180462B2 (en) |
| EP (1) | EP2393911B1 (en) |
| JP (1) | JP5599825B2 (en) |
| KR (1) | KR101770357B1 (en) |
| CN (1) | CN102307982B (en) |
| AR (1) | AR075502A1 (en) |
| BR (1) | BRPI1008871A2 (en) |
| CA (1) | CA2751428A1 (en) |
| CL (1) | CL2010000103A1 (en) |
| DK (1) | DK2393911T3 (en) |
| EA (1) | EA018932B1 (en) |
| ES (1) | ES2402710T3 (en) |
| HR (1) | HRP20130104T1 (en) |
| MX (1) | MX2011008274A (en) |
| PE (1) | PE20100693A1 (en) |
| PL (1) | PL2393911T3 (en) |
| PT (1) | PT2393911E (en) |
| SI (1) | SI2393911T1 (en) |
| WO (1) | WO2010090522A2 (en) |
| ZA (1) | ZA201105583B (en) |
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| GB201213777D0 (en) * | 2012-07-31 | 2012-09-12 | Internat Innovative Technologies Ltd | Mill apparatus with underslung mill units |
| CN103689769B (en) * | 2013-12-20 | 2015-08-19 | 黄山华绿园生物科技有限公司 | Food processing system |
| CN103736575B (en) * | 2014-01-24 | 2015-08-05 | 温州天龙机械科技有限公司 | With the nut protein extraction device of primary auxiliary teeth and air blowing agitating device |
| DE102014015549A1 (en) * | 2014-10-22 | 2016-04-28 | Thyssenkrupp Ag | Grinding plant for comminuting regrind and method for comminuting regrind |
| RU2585466C1 (en) * | 2015-02-26 | 2016-05-27 | Закрытое акционерное общество "Путь 910" | Method of producing activated suspension using disc crusher |
| US10337933B2 (en) * | 2015-04-17 | 2019-07-02 | Waters Technologies Corporation | Stirring paddle for isothermal titration calorimetry |
| JP6251433B1 (en) * | 2017-03-03 | 2017-12-20 | 株式会社大麦や | Processed barley product and process for producing processed barley product |
| CN107185426B (en) * | 2017-07-09 | 2023-06-20 | 贵州大学 | Raw material mixing device for beer production |
| AU2018312937B2 (en) | 2017-08-08 | 2022-09-29 | Kultevat, Inc. | System and method for continuous stirred tank solvent extraction using feedstock |
| EP4279162A3 (en) | 2017-08-08 | 2024-03-13 | Kultevat, Inc. | Rubber and by-product extraction systems and methods |
| JP2019046786A (en) * | 2017-09-04 | 2019-03-22 | 株式会社デンソー | Heater device |
| CN107890687A (en) * | 2017-09-22 | 2018-04-10 | 苏州雷度生物科技有限公司 | A kind of high-purity extraction equipment for plant extraction liquid |
| CN109022184A (en) * | 2018-11-05 | 2018-12-18 | 厦门华厦学院 | A kind of brewing sacchariferous equipment |
| CN109678973B (en) * | 2018-12-03 | 2021-03-12 | 安徽海逸生物科技有限公司 | Corn steep liquor recovery damage device of corn starch production |
| JP6651092B1 (en) * | 2019-03-11 | 2020-02-19 | 株式会社モキ製作所 | Separation device |
| RU2719508C1 (en) | 2019-10-21 | 2020-04-20 | Общество с ограниченной ответственностью "БиоВи" (ООО "БиоВи") | Albuminous cloudiness of brewer grains, method and apparatus for production thereof |
| CN111013772B (en) * | 2019-12-25 | 2021-11-30 | 新沂市中振电器科技有限公司 | Stem of noble dendrobium wine preparation is with cutting breaker |
| CN111889441B (en) * | 2020-08-12 | 2022-09-30 | 新疆阗丰农业科技有限责任公司 | All-in-one is smashed in washing of making wine raw materials |
| CN114433320A (en) * | 2022-02-09 | 2022-05-06 | 山东鲁碧建材有限公司 | Raw material grinds immediately and uses screw feeder with broken and safeguard function |
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| JP2579984B2 (en) * | 1988-01-28 | 1997-02-12 | 株式会社クボタ | Method for producing granular material and apparatus for producing the same |
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- 2010-02-05 CL CL2010000103A patent/CL2010000103A1/en unknown
- 2010-02-05 MX MX2011008274A patent/MX2011008274A/en active IP Right Grant
- 2010-02-05 PT PT107040073T patent/PT2393911E/en unknown
- 2010-02-05 AR ARP100100334A patent/AR075502A1/en active IP Right Grant
- 2010-02-05 EA EA201171003A patent/EA018932B1/en not_active IP Right Cessation
- 2010-02-05 CN CN2010800068752A patent/CN102307982B/en not_active Expired - Fee Related
- 2010-02-05 HR HRP20130104AT patent/HRP20130104T1/en unknown
- 2010-02-05 ES ES10704007T patent/ES2402710T3/en active Active
- 2010-02-05 JP JP2011549106A patent/JP5599825B2/en not_active Expired - Fee Related
- 2010-02-05 EP EP10704007A patent/EP2393911B1/en not_active Not-in-force
- 2010-02-05 US US13/147,783 patent/US9180462B2/en not_active Expired - Fee Related
- 2010-02-05 WO PCT/NL2010/050052 patent/WO2010090522A2/en not_active Ceased
- 2010-02-05 BR BRPI1008871-7A patent/BRPI1008871A2/en not_active IP Right Cessation
- 2010-02-05 CA CA2751428A patent/CA2751428A1/en not_active Abandoned
- 2010-02-05 KR KR1020117020757A patent/KR101770357B1/en not_active Expired - Fee Related
- 2010-02-05 PL PL10704007T patent/PL2393911T3/en unknown
- 2010-02-05 DK DK10704007.3T patent/DK2393911T3/en active
- 2010-02-05 SI SI201030140T patent/SI2393911T1/en unknown
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2011
- 2011-07-28 ZA ZA2011/05583A patent/ZA201105583B/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| DK2393911T3 (en) | 2013-04-15 |
| EP2393911A2 (en) | 2011-12-14 |
| EA201171003A1 (en) | 2012-01-30 |
| BRPI1008871A2 (en) | 2015-08-25 |
| JP2012516696A (en) | 2012-07-26 |
| MX2011008274A (en) | 2011-09-22 |
| EA018932B1 (en) | 2013-11-29 |
| HRP20130104T1 (en) | 2013-02-28 |
| KR20110127184A (en) | 2011-11-24 |
| PL2393911T3 (en) | 2013-06-28 |
| CA2751428A1 (en) | 2010-08-12 |
| CN102307982B (en) | 2013-10-16 |
| SI2393911T1 (en) | 2013-04-30 |
| US20120032007A1 (en) | 2012-02-09 |
| WO2010090522A3 (en) | 2011-04-07 |
| KR101770357B1 (en) | 2017-08-22 |
| US9180462B2 (en) | 2015-11-10 |
| CN102307982A (en) | 2012-01-04 |
| ES2402710T3 (en) | 2013-05-08 |
| PT2393911E (en) | 2013-04-23 |
| PE20100693A1 (en) | 2010-10-17 |
| ZA201105583B (en) | 2012-04-25 |
| JP5599825B2 (en) | 2014-10-01 |
| AR075502A1 (en) | 2011-04-06 |
| CL2010000103A1 (en) | 2010-05-14 |
| EP2393911B1 (en) | 2013-01-16 |
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